JP4777250B2 - Hydrogen production system and reformer - Google Patents

Description

  The present invention relates to a hydrogen production system and a reformer that can be used for industrial production of hydrogen from hydrocarbon-based raw materials.

  A hydrogen production system for industrially producing hydrogen includes a reforming reactor for generating a reformed gas (including hydrogen) by reforming a hydrocarbon-based raw material such as methanol or natural gas, An apparatus having an adsorption separation device for desorbing unnecessary components contained in the reformed gas and deriving a hydrogen-enriched gas is known. Further, as a reforming technique that can be employed in a reforming reactor of such a hydrogen production system, for example, a steam reforming method or a partial oxidation reforming method is known.

  In the steam reforming method, hydrogen is generated from the hydrocarbon raw material and water by a steam reforming reaction which is an endothermic reaction. For example, the thermochemical equation of the steam reforming reaction of methanol is represented by the following formula (1).

  Since the steam reforming reaction is an endothermic reaction, when only the steam reforming method is adopted as the reforming method in the reforming reactor of the hydrogen production system described above, a mixed raw material consisting of a hydrocarbon raw material and water is supplied. In order to allow the steam reforming reaction to proceed appropriately in the continuing reforming reactor, it is necessary to continue heating the reforming reactor. In addition, in such a steam reforming type hydrogen production system, the mixed raw material supplied into the reforming reactor is actually started at the start-up (the mixed raw material is subjected to the reforming reaction) so that the reforming reaction starts immediately. Before supplying to the reformer, the inside of the reforming reactor must be preheated to a desired temperature, and the mixed raw material must be heated to a high temperature vaporization state before being supplied to the reforming reactor. Such a steam reforming type hydrogen production system is described, for example, in Patent Document 1 below. In the hydrogen production system described in Patent Document 1, the combustion heat obtained by burning fuel (city gas) that is continuously supplied from the outside of the system is used in the reforming reactor and before being supplied to the reforming reactor. The mixed raw material is continuously heated. However, the configuration in which the external fuel must be combusted and the inside of the reforming reactor and the mixed raw material must be continuously heated is inefficient and easily causes an increase in hydrogen production cost. In addition, a hydrogen production system having a mechanism for burning external fuel and continuously heating the reforming reactor and the mixed raw material tends to be enlarged as a whole system, which is not preferable.

JP-A-9-309703

  On the other hand, in the partial oxidation reforming method, hydrogen is generated from the hydrocarbon-based raw material by a partial oxidation reforming reaction that is an exothermic reaction. For example, the thermochemical equation of the partial oxidation reforming reaction of methanol is expressed by the following formula (2).

  Since the partial oxidation reforming reaction is an exothermic reaction (not an endothermic reaction), in a hydrogen production system in which only the partial oxidation reforming method is adopted as the reforming method in the reforming reactor, the reforming reaction is performed in the reforming reactor. It is not necessary to continue heating the reforming reactor in order to proceed. However, the partial oxidation reforming reaction has a considerably lower hydrogen generation efficiency than the steam reforming reaction. Therefore, the partial oxidation reforming type hydrogen production system is not preferable from the viewpoint of hydrogen production efficiency. In addition, since the partial oxidation reforming reaction is an exothermic reaction, the partial oxidation reforming type hydrogen production system removes heat from the reforming reactor in order to maintain the reforming reactor at an appropriate reaction temperature. It is necessary to provide a heat removal mechanism to continue. The partial oxidation reforming type hydrogen production system that requires such a heat removal mechanism for the reforming reaction tends to be enlarged as a whole system, which is not preferable.

  The present invention has been conceived under such circumstances, and is a thermally self-supporting hydrogen production system capable of efficiently producing hydrogen, and part of such a hydrogen production system It is an object of the present invention to provide a reformer suitable for constituting the above.

  According to a first aspect of the present invention, a hydrogen production system is provided. This hydrogen production system is composed of a vaporizer for heating a mixed raw material containing hydrocarbon raw material, water and oxygen to a vaporized state, and a partial oxidation of the hydrocarbon raw material together with a steam reforming reaction of the hydrocarbon raw material. Pressure generated using a reforming reactor and an adsorption tower filled with an adsorbent for generating a reformed gas containing hydrogen from a mixed raw material in a vaporized state by causing reforming reactions simultaneously. By the variable adsorption gas separation method (PSA separation method), the reformed gas is introduced into the adsorption tower to adsorb unnecessary components in the reformed gas to the adsorbent, and the hydrogen-enriched gas is derived from the adsorption tower. A pressure fluctuation adsorption gas separation device (PSA separation device) for desorbing unnecessary components from the adsorbent and discharging a hydrogen-containing desorption gas containing hydrogen remaining in the adsorption tower and the unnecessary components from the adsorption tower. ). The vaporizer burns the hydrogen-containing desorption gas, and heats the mixed raw material using the combustion gas generated by the combustion as a heat source. During operation of the present hydrogen production system, a mixed raw material (including hydrocarbon-based raw material, water, and oxygen) is supplied to the vaporizer, and the mixed raw material is heated and vaporized in the vaporizer. The reformed reactor is supplied with the mixed raw material that has been vaporized through the vaporizer, and the reformed gas (including hydrogen) is generated from the mixed raw material in the reforming reactor. The reformed gas is supplied to the PSA separator, and the hydrogen-enriched gas and the hydrogen-containing desorbed gas are extracted from the reformed gas by the PSA separation method executed by the PSA separator. For example, the hydrogen-enriched gas is continuously used for a predetermined application or stored in a predetermined tank. The hydrogen-containing desorption gas is supplied to the vaporizer and used as a fuel for heating and vaporizing the mixed raw material in the vaporizer.

  Preferably, the hydrocarbon raw material used in the present hydrogen production system is methanol.

  Preferably, the hydrogen production system according to the present invention further includes a heating unit for heating the hydrocarbon-based raw material and water before being supplied to the vaporizer using the reformed gas as a heat source.

  Preferably, the vaporizer has a catalytic combustion section for catalytic combustion of the hydrogen-containing desorption gas.

  Preferably, the vaporizer has heat storage means for storing thermal energy of the combustion gas.

  As a preferred embodiment, the vaporizer has a main body container, a flow pipe for passing the mixed raw material, and a hydrogen containing desorption gas that is catalytically combusted to supply the combustion gas into the main body container. And a catalytic combustion section for

  Preferably, the vaporizer further includes a heat storage material filled in the main body container for storing thermal energy of the combustion gas. In this case, the heat storage material is preferably a ceramic ball.

  Preferably, the flow pipe has a spiral shape.

  Preferably, the apparatus further includes heating means for heating the reforming reactor using the combustion gas as a heat source.

  Preferably, the reforming reactor has a first region on the upstream side and a second region on the downstream side, and the first region and the second region are arranged adjacent to each other with a thermally conductive partition interposed therebetween. Has been.

  According to the second aspect of the present invention, there is provided a reformer for reforming a hydrocarbon-based raw material to generate a reformed gas. This reformer uses a combustion gas generated by burning fuel as a heat source, a vaporizer for heating a mixed raw material containing hydrocarbon raw material, water and oxygen to a vaporized state, and a hydrocarbon raw material. A reforming reactor for generating a reformed gas containing hydrogen from a mixed raw material in a vaporized state by causing a partial oxidation reforming reaction of a hydrocarbon-based raw material together with a steam reforming reaction. . In this case, the reforming reactor has a first region on the upstream side and a second region on the downstream side, and the first region and the second region are arranged adjacent to each other with a thermally conductive partition interposed therebetween. It is preferable. In the present reformer, the fuel preferably contains a part of hydrogen in the reformed gas.

  According to the third aspect of the present invention, there is provided a reformer for reforming a hydrocarbon-based raw material to generate a reformed gas. The present reformer is a catalyst for subjecting a mixed raw material containing a vaporized hydrocarbon raw material, water and oxygen to a partial oxidation reforming reaction of the hydrocarbon raw material together with a steam reforming reaction of the hydrocarbon raw material. And a reforming reactor for generating a reformed gas containing hydrogen from the mixed raw material in the vaporized state. This reforming reactor has a first region on the upstream side and a second region on the downstream side, and the first region and the second region are disposed adjacent to each other with a thermally conductive partition interposed therebetween. Yes. In this case, the partition wall is preferably composed of at least one tubular body.

1 is an overall schematic diagram of a hydrogen production system according to a first embodiment of the present invention. Fig. 2 shows an enlarged cross section of the vaporizer shown in Fig. 1. This enlarged cross section corresponds to a cross section taken along line II-II in FIG. It is a whole schematic diagram of the hydrogen production system concerning a 2nd embodiment of the present invention. It is sectional drawing along the IV-IV line of the reforming reactor shown in FIG. It is sectional drawing along the IVB-IVB line | wire of FIG. 4A. It is the same figure as FIG. 4A which shows the other example of a reforming reactor. It is sectional drawing which followed the VB-VB line | wire of FIG. 5A. It is the same figure as FIG. 4A which shows the other example of a reforming reactor. It is sectional drawing along the VIB-VIB line | wire of FIG. 6A. It is the same figure as FIG. 4A which shows the other example of a reforming reactor. It is sectional drawing along the VIIB-VIIB line | wire of FIG. 7A. It is a whole schematic diagram of the hydrogen production system concerning a 3rd embodiment of the present invention. It is a whole schematic diagram of the hydrogen production system concerning a 4th embodiment of the present invention. It is a graph showing the temperature distribution of the reforming reaction part in Examples 3 and 4 of the present invention.

  1 and 2 show a hydrogen production system X1 according to the first embodiment of the present invention. FIG. 1 shows a schematic configuration of the entire hydrogen production system X1. FIG. 2 shows a cross section taken along line II-II shown in FIG.

  The hydrogen production system X1 includes a reformer Y1 in which a vaporizer 1 and a reformer reactor 2 are connected in the vertical direction, a heat exchanger 3, a gas-liquid separator 4, and a pressure fluctuation adsorption gas separator (PSA separator). 5), and is configured to produce hydrogen using methanol, which is a hydrocarbon-based material, as a main material.

  The vaporizer 1 of the reformer Y1 includes a main body container 11, a supply pipe 12, a catalyst combustion unit 13, a flow pipe 14, and a heat storage material 15 (see FIG. 2), methanol and water, This is for heating the mixed raw material containing oxygen into a vaporized state. In addition, in FIG. 1, while showing a part by sectional shape from a viewpoint of clarifying the internal structure of the vaporizer | carburetor 1, the heat storage material 15 is abbreviate | omitted.

  The main body container 11 has a closed end tubular structure, and a combustion gas discharge port 111 is provided at an upper end portion thereof. Examples of the material constituting the main body container 11 include stainless steel.

  The supply pipe 12 has a double pipe structure including an outer pipe 121 and an inner pipe 122. The outer pipe 121 has an upper end connected to the pipe 61 outside the main body container 11, and a lower end opened in the main body container 11. The inner pipe 122 has an upper end connected to the pipe 63 and the pipe 72 outside the main body container 11, and a lower end opened in the outer pipe 121. The pipe 61 connected to the outer pipe 121 is also connected to the air blower 62. A pipe 63 connected to the inner pipe 122 is connected to a supply source (not shown) of vaporizing fuel (for example, LPG) for starting operation, and this pipe 63 is provided with an automatic valve 63a. Yes.

  The catalytic combustion unit 13 is provided at the lower end portion in the outer pipe 121 of the supply pipe 12 and is a part for generating high-temperature combustion gas by catalytic combustion of hydrogen or the above-mentioned start-up fuel. The catalyst combustion section 13 is filled with a combustion catalyst. Examples of the combustion catalyst include platinum-based catalysts such as platinum and palladium.

  The flow pipe 14 has a raw material inlet end 141 and a raw material outlet end 142, and has a spiral shape that partially surrounds the supply pipe 12. The raw material introduction end 141 and the raw material outlet end 142 respectively protrude from the lower end portion of the main body container 11 to the outside of the main body container 11. Examples of the material constituting the flow pipe 14 include stainless steel.

  As shown in FIG. 2, the heat storage material 15 is filled around the supply pipe 12 and the circulation pipe 14 in the main body container 11. Here, in the main body container 11, a gap through which the combustion gas generated in the catalytic combustion unit 13 can pass is ensured between the supply pipe 12 and the flow pipe 14 and the heat storage material 15. The heat storage material 15 has a heat capacity larger than that of the main body container 11 and the flow pipe 14 and is preferably substantially spherical, and examples thereof include ceramic balls.

  The reforming reactor 2 of the reforming apparatus Y1 includes a main body container 21 and a reforming reaction section 22 as shown in FIG. The reforming reactor 2 reforms the methanol in the mixed raw material that has been vaporized in the vaporizer 1 by simultaneously performing a steam reforming reaction and a partial oxidation reforming reaction of methanol, and reforms containing hydrogen. It is for producing quality gas.

  The main body container 21 has a closed-end tubular structure, a raw material inlet 211 is provided at one end thereof, and a reformed gas outlet 212 is provided at the other end. The raw material inlet 211 is connected to the raw material outlet end 142 of the vaporizer 1 described above. Examples of the material constituting the main body container 21 include stainless steel.

The reforming reaction unit 22 is provided inside the main body container 21 and is a part filled with a reforming catalyst (not shown). This reforming catalyst is for causing the steam reforming reaction and the partial oxidation reforming reaction to co-occur on methanol in the mixed raw material in the vaporized state. As the reforming catalyst, for example, a mixture containing aluminum oxide, copper oxide and zinc oxide can be employed. The content ratio of the above components in the reforming catalyst is, for example, 42 wt% for CuO, 47 wt% for ZnO, and 10 wt% for Al ₂ O ₃ .

  The heat exchanger 3 has a methanol water inlet 31, a methanol water outlet 32, a reformed gas inlet 33, and a reformed gas outlet 34 before being supplied to the vaporizer 1. This is for preheating the methanol water and cooling the reformed gas by heat exchange between the methanol water and the reformed gas generated in the reforming reactor 2. In the heat exchanger 3, a path for methanol water to flow from the methanol water inlet 31 to the methanol water outlet 32 and a reformed gas to flow from the reformed gas inlet 33 to the reformed gas outlet 34. These paths are provided, and heat exchange is possible between these two types of paths. Such a heat exchanger 3 contributes to reducing the heat energy required when the mixed raw material is heated to the vaporized state in the vaporizer 1. In addition, according to such a heat exchanger 3, the reformed gas can be removed (cooled), so the hydrogen production system X1 needs to include a cooling device for cooling the reformed gas. There is no.

  The methanol water inlet 31 is connected to a methanol water supply source (not shown) via a pipe 64 and a pump 65. The pump 65 is for sending methanol water at a predetermined pressure (for example, 0.9 MPa). The methanol water outlet 32 is connected to the raw material introduction end 141 of the vaporizer 1 through a pipe 66. A pipe 67 is connected to the pipe 66 through one end thereof. The other end of the pipe 67 is connected to a supply source (not shown) of an oxygen-containing gas (for example, oxygen-enriched gas or air). The pipe 67 is provided with a flow rate adjusting valve 67a for adjusting the flow rate of the oxygen-containing gas. The reformed gas inlet 33 is connected to the reformed gas outlet 212 of the reforming reactor 2 through a pipe 68. The reformed gas outlet 34 is connected to a gas-liquid separator 4 to be described later via a pipe 69.

  The gas-liquid separator 4 has a liquid discharge port 41 and is for gas-liquid separation of a liquid component (for example, water) 42 mixed in the reformed gas from the gas. The liquid discharge port 41 is for discharging the liquid component 42 collected by the gas-liquid separator 4 to the outside of the gas-liquid separator 4.

  The PSA separation device 5 includes at least one adsorption tower filled with an adsorbent, and can extract a hydrogen-enriched gas from the reformed gas by a pressure fluctuation adsorption gas separation method performed using the adsorption tower. is there. As the adsorbent packed in the adsorption tower, for example, a zeolite adsorbent, a carbon adsorbent, or an alumina adsorbent can be employed, and a zeolite adsorbent is preferably employed. A single adsorption tower may be filled with one kind of adsorbent, or may be filled with plural kinds of adsorbents. In the pressure fluctuation adsorption type gas separation method executed in the PSA separation device 5, one cycle including an adsorption step, a desorption step, and a regeneration step is repeated for a single adsorption tower. In the adsorption process, the reformed gas is introduced into an adsorption tower having a predetermined high pressure inside the tower, and unnecessary components (carbon monoxide, carbon dioxide, unreacted methanol, nitrogen, etc.) in the reformed gas are adsorbed. It is a process for deriving hydrogen-enriched gas from the adsorption tower. The desorption step is a step for depressurizing the inside of the adsorption tower to desorb unnecessary components from the adsorbent and discharging the unnecessary components outside the tower. The regeneration step is a step for recovering the adsorption performance of the adsorbent with respect to unnecessary components, for example, by passing a cleaning gas through the tower in order to provide the adsorption column in the second adsorption step. As such a PSA separator 5, a known PSA hydrogen separator can be used.

  Next, an example of a specific operation of the hydrogen production system X1 having the above configuration will be described.

  When the hydrogen production system X1 is in operation, the pump 65 is activated, whereby methanol water of a predetermined concentration is introduced into the heat exchanger 3 from the methanol water inlet 31 via the pipe 64. In the heat exchanger 3, the relatively low temperature (for example, 10 to 25 ° C.) methanol water is introduced into the heat exchanger 3 as described later, and the relatively high temperature (for example, 230 to 270 ° C.) For example, it is heated (preheated) to 137 ° C. by heat exchange with the gas. The methanol water preheated in the heat exchanger 3 is led out of the heat exchanger 3 from the methanol water outlet 32 and is introduced into the pipe 66 through the pipe 67 when passing through the pipe 66 ( For example, it is mixed with oxygen-enriched gas or air). The supply amount of the oxygen-containing gas can be adjusted by the flow rate adjustment valve 67a.

  The mixed raw material (including methanol, water, and oxygen) thus obtained is introduced from the raw material introduction end 141 into the flow pipe 14 of the vaporizer 1. The mixed raw material introduced into the flow pipe 14 passes through the flow pipe 14, and the reforming reaction in the subsequent reforming reactor 2 using the combustion gas generated in the catalytic combustion section 13 as a heat source as described later. And is vaporized by being heated to a desired reaction temperature (for example, 230 to 270 ° C.) required in the above. The mixed raw material in a vaporized state is led out of the vaporizer 1 from the raw material outlet end 142 of the flow pipe 14 and supplied to the reforming reactor 2 through the raw material inlet 211.

  The mixed raw material supplied to the reforming reactor 2 is introduced into the reforming reaction unit 22. In the reforming reaction section 22, by the action of the reforming catalyst, a steam reforming reaction of methanol which is an endothermic reaction and a partial oxidation reforming reaction of methanol which is an exothermic reaction occur simultaneously, and reforming including hydrogen from the mixed raw material. Gas is generated. In the present embodiment, the ratio of methanol consumed in each reaction (that is, the ratio of each reaction) is set so that the reaction temperature (for example, 230 to 270 ° C.) in the reforming reaction unit 22 is maintained substantially constant. ing. That is, in the reforming reaction unit 22, the autothermal reforming reaction of methanol proceeds.

The steam reforming reaction and partial oxidation reforming reaction of methanol are represented by the above formulas (1) and (2), respectively, and the endothermic amount (Q ₁ ) of the steam reforming reaction per 1 mol of methanol consumption. Is 49.5 kJ, and the calorific value (Q ₂ ) of the partial oxidation reforming reaction per mol of methanol consumed is 192.5 kJ. In the present embodiment, the ratio of the steam reforming reaction and the partial oxidation reforming reaction is adjusted so that the sum of Q ₁ and the amount of heat loss (Q ₃ ) to the outside of the reforming reaction unit 22 matches Q _2. Thereby, the inside of the reforming reaction section 22 is maintained at a desired reaction temperature. The ratio of the steam reforming reaction and the partial oxidation reforming reaction can be adjusted, for example, by adjusting the composition of the mixed raw material supplied to the reforming reactor 2 or the reforming reaction unit 22. For example, in the case of Q ₃ = 0, assuming that the ratio of the steam reforming reaction is x and the ratio of the partial oxidation reforming reaction is 1-x, the values of x and 1-x can be obtained by the following equation: it can. That is, when Q ₃ = 0, the steam reforming reaction ratio x is about 0.80, and the partial oxidation reforming reaction ratio 1-x is about 0.20. it can.

  The reformed gas generated in the reforming reaction section 22 is led out of the reforming reactor 2 from the reformed gas outlet 212 and introduced into the heat exchanger 3 through the pipe 68 and the reformed gas inlet 33. The In the heat exchanger 3, the relatively high temperature (for example, 230 to 270 ° C.) reformed gas is introduced into the heat exchanger 3 as described above and has a relatively low temperature (for example, 10 to 25 ° C.). It is cooled to, for example, 40 ° C. by heat exchange with methanol water. The reformed gas cooled in the heat exchanger 3 is led out of the heat exchanger 3 from the reformed gas outlet 34 and introduced into the gas-liquid separator 4 through the pipe 69.

  In the reformed gas introduced into the gas-liquid separator 4, the liquid component 42 mixed in the reformed gas is gas-liquid separated from the reformed gas. Thereby, it can suppress that the liquid component 42 is introduce | transduced into the adsorption tower of the PSA separation apparatus 5 located downstream of the gas-liquid separator 4. FIG. Therefore, the deterioration of the adsorbent due to the liquid component 42 coming into contact with the adsorbent packed in the adsorption tower can be suppressed. The liquid component 42 recovered by the gas-liquid separation is discharged from the gas-liquid separator 4 to the outside through the liquid discharge port 41. The reformed gas that has passed through the gas-liquid separator 4 is supplied to the PSA separator 5 via the pipe 70.

  In the PSA separation apparatus 5, one cycle including an adsorption step, a desorption step, and a regeneration step is repeated for each adsorption tower by the pressure fluctuation adsorption gas separation method.

  In the adsorption step, a reformed gas containing hydrogen is introduced into an adsorption tower whose inside is in a predetermined high pressure state. In the adsorption tower, unnecessary components (carbon monoxide, carbon dioxide, unreacted methanol, nitrogen, etc.) contained in the reformed gas are adsorbed and removed by the adsorbent, and hydrogen-enriched gas (gas with high hydrogen concentration) is the product. It is led out of the tower as gas. This hydrogen-enriched gas is taken out of the hydrogen production system X1 through the pipe 71. In the desorption step, unnecessary components are desorbed from the adsorbent due to reduced pressure in the tower, and hydrogen-containing desorbed gas containing hydrogen remaining in the tower and the unnecessary components is discharged outside the tower. This hydrogen-containing desorption gas is supplied as vaporization fuel from the adsorption tower to the vaporizer 1 via the pipe 72. In the regeneration process, for example, the cleaning gas is passed through the tower, so that the adsorption performance of the adsorbent with respect to unnecessary components is recovered. From the PSA separation device 5, the hydrogen-enriched gas (product gas) is taken out and the hydrogen-containing desorption gas is taken out as described above. For example, the hydrogen-enriched gas is continuously used for a predetermined application or stored in a predetermined tank.

  The hydrogen-containing desorption gas supplied to the vaporizer 1 as a vaporizing fuel is introduced into the catalytic combustion unit 13 through the inner pipe 122 and the outer pipe 121. At the same time, air continues to be supplied to the catalytic combustion unit 13. Specifically, air is continuously supplied to the catalytic combustion unit 13 through the pipe 61 and the outer pipe 121 by the operation of the blower 62. In such a catalytic combustion section 13, the hydrogen in the hydrogen-containing desorption gas is catalytically burned by the action of the combustion catalyst, and high-temperature (for example, 500 to 600 ° C.) combustion gas is generated. In catalytic combustion, since the range of the combustion temperature at which combustion can be maintained is relatively large, stable combustion can be maintained even if the hydrogen content of the hydrogen-containing desorption gas varies somewhat. Further, since catalytic combustion hardly generates incomplete combustion gas, the environmental load due to the final release of the combustion gas generated in the vaporizer 1 into the atmosphere is small.

  The high-temperature combustion gas generated in the catalytic combustion unit 13 is released from the open end (lower end in the figure) of the outer pipe 121 of the supply pipe 12 and passes through the location where the heat storage material 15 is filled in the main body container 11. Then, it is discharged out of the vaporizer 1 from the combustion gas discharge port 111. When the combustion gas passes through the filling portion of the heat storage material 15, heat energy is transferred from the combustion gas as a heat source to the flow pipe 14, and the mixed raw material flowing through the flow pipe 14 reaches a predetermined temperature (for example, 230 to 270 ° C.). It is heated and vaporized. Since the flow pipe 14 has a spiral shape, a large surface area (heat receiving area) of the flow pipe 14 can be secured. Therefore, the circulation pipe 14 having such a spiral shape increases the heat transfer efficiency with respect to the mixed raw material flowing through the distribution pipe 14 and contributes to efficiently heating the mixed raw material.

  Here, when the temperature of the combustion gas is higher than the temperature of the heat storage material 15, the heat energy from the combustion gas is also transmitted to the heat storage material 15 and stored in the heat storage material 15, and the temperature of the combustion gas is the heat storage material. When the temperature is lower than 15, the combustion gas can be heated using the heat storage material 15 as a heat source. Therefore, the heat storage material 15 can alleviate temperature fluctuations of the combustion gas that functions as a heat source for heating the mixed raw material, and accordingly, the mixed raw material can be appropriately heated to be in a vaporized state. In addition, since the combustion gas flows through a narrow gap generated between the heat storage materials 15 in the main body container 11, the flow velocity becomes larger than when the heat storage material 15 is not filled. Therefore, the heat storage material 15 contributes to increasing the heat transfer efficiency of the combustion gas with respect to the mixed raw material and efficiently heating the mixed raw material.

  As described above, in the hydrogen production system X1, during its steady operation, the raw materials are the heat exchanger 3, the vaporizer 1, the reforming reactor 2, the heat exchanger 3, the gas-liquid separator 4, and the PSA separator. 5 sequentially, the hydrogen-enriched gas is taken out from the PSA separator 5 and the hydrogen-containing desorbed gas discharged from the PSA separator 5 is supplied to the vaporizer 1.

  Note that the specific operation of the hydrogen production system X1 described above is the operation during steady operation in which the hydrogen-containing desorption gas is sufficiently supplied from the PSA separator 5 to the catalytic combustion unit 13, for example. At start-up, the hydrogen-containing desorption gas is not sufficiently supplied from the PSA separator 5 to the catalytic combustion unit 13. In such a case, the automatic combustion valve 63a is kept open until the hydrogen-containing desorption gas can be sufficiently supplied from the PSA separator 5 to the catalytic combustion unit 13, for example, in the catalytic combustion unit 13. Necessary vaporizing fuel (for example, LPG) is supplementarily supplied to the vaporizer 1 or its catalytic combustion unit 13.

  In the hydrogen production system X1, by adjusting the supply amount (supply amount per unit time) of the hydrogen-containing desorption gas discharged from the PSA separation device 5 and supplied to the vaporizer 1 at the time of operation, the hydrogen production system X1 is predetermined. At the time of steady operation after the lapse of the period, only the hydrogen-containing desorption gas from the PSA separation device 5 is provided for the fuel necessary for heating the mixed raw material in the vaporizer 1 to a vaporized state at a desired temperature. Further, in the hydrogen production system X1, the reforming is performed by adjusting the ratio of the steam reforming reaction and the partial oxidation reforming reaction of the hydrocarbon raw material that proceeds in the reforming reaction section 22 of the reforming reactor 2 during its operation. The inside of the reactor is maintained at a desired reaction temperature. Thus, during the steady operation of the hydrogen production system X1, the mixed raw material is continuously heated and vaporized only by the self-supplied heat accompanying the system operation, and the reforming reaction section 22 of the reforming reactor 2 is maintained at the desired temperature. Has been. According to such a heat self-supporting hydrogen production system, it is possible to efficiently produce hydrogen by avoiding an inefficient method or configuration in which external fuel is burned to continuously heat the mixed raw material and the reforming reactor. Can do. Such efficiency improvement is suitable for reducing the hydrogen production cost, for example.

  In addition, as described above, the hydrogen production system X1 capable of realizing the autothermal reforming reaction by balancing the heat balance in the reforming reactor 2 burns external fuel and heats the reforming reactor 2 inside. Therefore, it is not necessary to separately provide a heating mechanism for heat removal and a heat removal mechanism for removing heat inside the reforming reactor 2, which is suitable for making the system compact. Further, since the hydrogen production system X1 employs the steam reforming reaction together with the partial oxidation reforming reaction as the reforming method in the reforming reactor 2, the reforming reactor is more effective than the partial oxidation reforming type hydrogen production system. The production efficiency of hydrogen at 2 is high. In addition, in the hydrogen production system X1, since a partial oxidation reforming reaction that is an exothermic reaction proceeds together with a steam reforming reaction that is an endothermic reaction in the reforming reactor 2, as in a steam reforming type hydrogen production system. It is not necessary to raise the temperature inside the reforming reactor 2 in advance to the minimum required reaction temperature or higher. Therefore, this hydrogen production system can be started up in a relatively short time.

  3, 4A and 4B show a hydrogen production system X2 according to the second embodiment of the present invention. FIG. 3 shows a schematic configuration of the entire hydrogen production system X2. FIG. 4A represents a cross section taken along line IV-IV in FIG. FIG. 4B represents a cross section taken along line IVB-IVB in FIG. 4A. In the second embodiment of the present invention, the same or similar members and parts as those in the first embodiment of the present invention are denoted by the same reference numerals, and description thereof will be omitted as appropriate.

  The hydrogen production system X2 includes a reformer Y2 composed of a vaporizer 1 and a reforming reactor 2A, a heat exchanger 3, a gas-liquid separator 4, and a PSA separator 5, and is a hydrocarbon-based raw material. Hydrogen is produced using methanol as a main raw material.

  As shown in FIGS. 4A and 4B, the reforming reactor 2A includes a main body container 21, a tube body 23, and a reforming reaction section 22A. The reforming reactor 2A includes a tube body 23, a point having a reforming reaction unit 22A instead of the reforming reaction unit 22, and a point in which various design changes are made accordingly. This is different from the reforming reactor 2 in the first embodiment.

  In the present embodiment, the main body container 21 is provided with a raw material inlet 211 at its upper end and a reformed gas outlet 212 at a side wall near the upper end.

  As shown in FIGS. 4A and 4B, the tube body 23 has a cylindrical shape having a certain thickness, and is provided inside the main body container 21. The upper end portion of the tube body 23 is attached to the inner surface of the upper end portion of the main body container 21 by a technique such as welding. The upper end portion of the tube body 23 communicates with the raw material inlet 211, and there is no gap between the upper end portion of the tube body 23 and the inner surface of the upper end portion of the main body container 21. A lower end portion of the tube body 23 is opened in the main body container 21. Thereby, in the inside of the main body container 21, the raw material introduction port 211 passes through the inside of the pipe body 23, the lower part of the main body container 21, and between the main body container 21 and the pipe body 23 to the reformed gas outlet port 212. A path through which the gas reaches is formed. The tube body 23 is made of a material having thermal conductivity. Examples of the material constituting the tube body 23 include stainless steel having excellent thermal conductivity.

  The reforming reaction part 22A is a part filled with a reforming catalyst, and has a cylindrical first region 221 located inside the tube body 23, and the tube body 23 sandwiched between the first region 221. It is comprised from the cylindrical 2nd area | region 222 which adjoins and positions (between the main body container 21 and the pipe body 23). The first region 221 is defined by the tube body 23 and a pair of partition members 223 provided on the inner side of the tube body 23 so as to be separated in the vertical direction. The second region 222 is defined by the main body container 21, the tube body 23, and a pair of partition members 224 provided in the vertical direction between the main body container 21 and the tube body 23. That is, the tube body 23 serves as a partition wall that partitions the adjacent first region 221 and second region 222. As the partition members 223 and 224, those capable of containing the reforming catalyst while allowing the mixed raw material and reformed gas in a vaporized state to pass through are used, and examples thereof include a punching plate.

  In the hydrogen production system X2, as in the hydrogen production system X1, during the steady operation thereof, the raw materials are heat exchanger 3, vaporizer 1, reforming reactor 2A, heat exchanger 3, gas-liquid separator 4, and By sequentially passing through the PSA separation device 5, the hydrogen-enriched gas is taken out from the PSA separation device 5, and the hydrogen-containing desorption gas discharged from the PSA separation device 5 is supplied to the vaporizer 1.

  In the hydrogen production system X2, the vaporized mixed raw material supplied to the reforming reactor 2A via the raw material introduction port 211 passes through the first region 221 on the upstream side located inside the tubular body 23, and the tubular body. The gas is discharged from the lower end of the main body 23, passes through the second region 222 on the downstream side located between the main body container 21 and the pipe body 23, and is guided to the reformed gas outlet 212. The arrows shown in FIG. 4B indicate the direction of gas flow in the main body container 21 (this is the same for FIGS. 5B, 6B, and 7B described later). In the reforming reaction section 22A (first region 221 and second region 222), the autothermal reforming reaction of methanol proceeds by the action of the reforming catalyst, and reformed gas containing hydrogen is generated from the mixed raw material. .

  By the way, when the steam reforming reaction and partial oxidation reforming reaction of methanol occur simultaneously, the reaction rate of the partial oxidation reforming reaction, which is an exothermic reaction, is comparable to the reaction rate of the steam reforming reaction, which is an endothermic reaction. fast. Therefore, when mixed raw materials are introduced into the reforming reaction section, the partial oxidation reforming reaction proceeds mainly in the upstream area of the reforming reaction section and the temperature rises, while the downstream area of the reforming reaction section. In this case, the temperature is lowered mainly due to the steam reforming reaction. That is, even if the autothermal reforming reaction is performed as a whole in the reforming reaction part, the temperature of each part varies. If there is a portion that is lower than the temperature required for the steam reforming reaction in the region downstream of the reforming reaction section, the steam reforming reaction cannot sufficiently proceed, and the amount of hydrogen generated is reduced. . Further, when the temperature in the upstream region of the reforming reaction section becomes extremely high, the activity of the reforming catalyst is impaired, and the amount of hydrogen generated decreases.

  On the other hand, in the present embodiment, in the reforming reaction section 22A, the upstream first region 221 and the downstream second region 222 are adjacent to each other with the thermally conductive tube 23 interposed therebetween. For this reason, heat energy is transmitted through the tube body 23 from the first region 221 having a relatively high temperature to the second region 222 having a relatively low temperature (the black arrows shown in FIGS. 4A and 4B are , Shows the direction of heat transfer through the tube body 23. The same applies to FIGS. 5A to 7B described later.), The temperature distribution of each part in the reforming reaction part 22A is leveled. As a result, the entire downstream second region 222 is maintained at a temperature higher than that necessary for the steam reforming reaction, and the steam reforming reaction continues to sufficiently proceed. Further, in the first region 221 on the upstream side, an extremely high temperature due to heat transfer to the second region 222 is avoided.

  Furthermore, since the reforming reaction section 22A is partitioned into the first region 221 and the second region 222 by the tube body 23, gas (vaporized mixed raw material or reforming) is obtained as compared with the case where the tube body 23 is not provided. The cross sectional area of the gas) is reduced. Therefore, the flow rate of the gas passing through the reforming reaction portion 22A is larger than that when the tube body 23 is not provided. This increases the heat transfer efficiency due to the movement of the gas from the upstream side to the downstream side of the reforming reaction section 22A, and contributes to more appropriate leveling of the temperature distribution in the reforming reaction section 22A.

  As described above, in the configuration in which the first region 221 on the upstream side and the second region 222 on the downstream side of the reforming reaction section 22A are arranged adjacent to each other with the thermally conductive tube body 23 (partition wall) interposed therebetween, endothermic heat is absorbed. The variation in temperature distribution of each part of the reforming reaction part 22A due to the difference in reaction rate between the steam reforming reaction which is a reaction and the partial oxidation reforming reaction which is an exothermic reaction is eliminated. According to the hydrogen production system X2 having the reforming reactor 2A having such a configuration, the steam reforming reaction and the partial oxidation reforming reaction can be appropriately advanced, which is suitable for further increasing the hydrogen generation efficiency. .

  5A to 7B show a modification of the reforming reactor in the present embodiment.

  In the reforming reactor 2B shown in FIGS. 5A and 5B, the raw material inlet 211 is provided on the side wall near the upper end of the main body container 21 and the reformed gas outlet 212 is provided on the upper end of the main body container 21. It has been. In the reforming reaction part 22B of the reforming reactor 2B, the space between the main body container 21 and the tube body 23 corresponds to the first region 221 on the upstream side, and the inside of the tube body 23 corresponds to the second region 222 on the downstream side. Equivalent to. That is, the reforming reactor 2B is different from the reforming reactor 2 shown in FIGS. 4A and 4B in that the positional relationship between the first region 221 and the second region 222 is reversed.

  In the reforming reactor 2C shown in FIGS. 6A and 6B, instead of the single tube body 23 in the first embodiment, a plurality of (seven) tube bodies 23 communicating with the raw material inlet 211 are provided. Is provided. In the reforming reaction section 22C of the reforming reactor 2C, the inside of the tube body 23 corresponds to the upstream first region 221 and the space between the main body container 21 and the tube body 23 is the second downstream side. This corresponds to the region 222. That is, in the reforming reaction part 22C, the upstream first region 221 is dispersed and arranged inside the plurality of tubes 23. According to such a configuration, a large heat receiving area of the tube body 23 that functions as a heat conducting portion can be secured. Therefore, when the partial oxidation reforming reaction proceeds together with the steam reforming reaction, the heat transfer efficiency from the first region 221 to the second region 222 is increased via the tube body 23, and the temperature distribution in the reforming reaction unit 22C. Is more appropriately leveled. This also contributes to further increasing the efficiency of hydrogen generation by allowing the steam reforming reaction and the partial oxidation reforming reaction to proceed more appropriately.

  In the reforming reactor 2D shown in FIGS. 7A and 7B, a flat partition wall 23D is provided instead of the tube body 23. The raw material inlet 211 is provided at the upper end (left side in the figure) of the main body container 21, and the reformed gas outlet 212 is provided at the upper end (right side in the figure) of the main body container 21. The partition wall 23 </ b> D is fixed to the inner surface of the main body container 21 so as to have a predetermined opening between the lower end portion of the main body container 21. In the reforming reaction section 22D of the reforming reactor 2D, the left portion in the drawing corresponds to the upstream first region 221 with respect to the partition wall 23D, and the right portion in the drawing is downstream with respect to the partition wall 23D. Corresponds to the second region 222.

  FIG. 8 shows a schematic configuration of the entire hydrogen production system X3 according to the third embodiment of the present invention. In the third embodiment of the present invention, the same or similar members and parts as those in the first embodiment of the present invention are denoted by the same reference numerals, and description thereof will be omitted as appropriate.

  The hydrogen production system X3 includes a reformer Y3 including a vaporizer 1 and a reformer reactor 2, a heat exchanger 3, a gas-liquid separator 4, and a PSA separator 5, and is a hydrocarbon-based raw material. Hydrogen is produced using methanol as a main raw material.

  In the reformer Y3, the positional relationship between the vaporizer 1 and the reforming reactor 2 is reversed upside down, and various design changes have been made to the vaporizer 1 and the reforming reactor 2 accordingly. This is different from the reformer Y1. In this embodiment, the supply pipe 12 of the vaporizer 1 extends from the side wall of the main body container 11 to the outside. A raw material outlet end 142 of the flow pipe 14 protrudes from the upper end portion of the main body container 11 to the outside of the main body container 11. The raw material inlet 211 and the reformed gas outlet 212 of the reforming reactor 2 are provided at the lower end and the upper end of the main body container 21, respectively.

  In the hydrogen production system X3, as in the hydrogen production system X1, during the steady operation, the raw materials are converted into the heat exchanger 3, the vaporizer 1, the reforming reactor 2, the heat exchanger 3, the gas-liquid separator 4, and By sequentially passing through the PSA separation device 5, the hydrogen-enriched gas is taken out from the PSA separation device 5, and the hydrogen-containing desorption gas discharged from the PSA separation device 5 is supplied to the vaporizer 1.

  Further, in the hydrogen production system X3, as described above, the raw material inlet 211 for receiving the mixed raw material connected to the raw material outlet end 142 in the vaporizer 1 is provided at the lower end portion of the reforming reactor 2. . Therefore, even if the mixed raw material in the vaporizer 1 is not sufficiently heated and a part of the mixed raw material is not in a vaporized state, the mixed raw material that is not in the vaporized state is mixed with the mixed raw material inlet. It is difficult to come into contact with the reforming catalyst filled in the reforming reaction unit 22 located above 211. Therefore, in the hydrogen production system X3, deterioration of the reforming catalyst due to the mixed raw material not in a vaporized state coming into contact with the reforming catalyst is suppressed. The hydrogen production system X3 has such advantages in addition to the advantages described above with respect to the hydrogen production system X1.

  FIG. 9 shows a schematic configuration of the entire hydrogen production system X4 according to the fourth embodiment of the present invention. In the fourth embodiment of the present invention, the same or similar members and parts as those in the first embodiment of the present invention are denoted by the same reference numerals, and description thereof will be omitted as appropriate.

  The hydrogen production system X4 includes a reformer Y4 including a vaporizer 1 and a reforming reactor 2 ′, a heat exchanger 3, a gas-liquid separator 4, and a PSA separator 5, and is made of a hydrocarbon-based raw material. It is configured to produce hydrogen using a certain methanol as a main raw material. The hydrogen production system X4 differs from the hydrogen production system X1 in that a reformer Y4 is provided instead of the reformer Y1, and the reformer Y4 is replaced with a reformer reactor 2 ′ instead of the reformer reactor 2. Is different from the reforming apparatus Y1.

  The reforming reactor 2 ′ has a main body container 21, a reforming reaction part 22, and a jacket part 24. The jacket portion 24 has a combustion gas introduction port 241 and a combustion gas discharge port 242, and is configured to surround the outer periphery of the main body container 21 of the reforming reactor 2 '. The combustion gas introduction port 241 is for introducing the combustion gas discharged from the combustion gas discharge port 111 of the carburetor 1 into the jacket portion 24, and is connected to the combustion gas discharge port 111 via the pipe 243. . The combustion gas discharge port 242 is for discharging the combustion gas in the jacket portion 24 to the outside.

  In the hydrogen production system X4, as in the hydrogen production system X1, the hydrogen-enriched gas is taken out from the PSA separation device 5 when the raw material sequentially passes through each part of the system during its steady operation, and the PSA separation device The hydrogen-containing desorption gas discharged from 5 is supplied to the vaporizer 1.

  Further, during operation of the hydrogen production system X4, a relatively high temperature (for example, 300 ° C.) combustion gas discharged from the combustion gas discharge port 111 of the vaporizer 1 is introduced into the jacket portion 24 via the pipe 243. The The combustion gas introduced into the jacket portion 24 heats the reforming reactor 2 '. And the combustion gas in the jacket part 24 is discharged | emitted outside via the combustion gas discharge port 242.

In the hydrogen production system X4, the reforming reactor 2 ′ can be heated using the combustion gas as a heat source, and therefore the inside of the reforming reaction section 22 that is reduced by radiating heat from the main body container 21 of the reforming reactor 2 ′. The heat energy can be supplemented. For example, all of the heat loss (Q ₃ ) described above with respect to the first embodiment can be supplemented with the heat amount of the combustion gas introduced into the jacket portion 24. When all of the loss of heat (Q ₃ ) is supplemented by the amount of heat of the combustion gas introduced into the jacket portion 24, the endothermic amount (Q ₁ ) due to the steam reforming reaction and the exothermic amount (Q ₂ ) due to the partial oxidation reforming reaction Thus, the autothermal reforming reaction with the heat balance of zero set to zero can be continued appropriately. Further, in the hydrogen production system X4, a heat quantity exceeding the loss heat quantity (Q ₃ ) may be supplied from the jacket part 24 to the reforming reaction part 22 in the reforming reactor 2 ′. In this case, even if the ratio of the steam reforming reaction in the autothermal reforming reaction (the value of x described above) is set significantly higher than 0.80, the autothermal reforming reaction should continue to proceed appropriately. And the production efficiency of hydrogen can be increased.

  The present invention is not limited to the contents of the above-described embodiment. The specific configuration of each part of the hydrogen production system and the reformer according to the present invention can be varied in design in various ways. For example, it is good also as a structure which does not provide the thermal storage material as a thermal storage means.

  Hydrogen (hydrogen-enriched gas) was produced from a mixed raw material (including methanol, water and oxygen) using a hydrogen production system X1 having the following specific configuration.

[Hydrogen production system]
In the hydrogen production system of the present example, the main body container 11 of the vaporizer 1 was constituted by a stainless steel tube (outer diameter: 216 mm, inner diameter: 208 mm, overall length: 1000 mm). As the catalyst combustion section 13, a predetermined combustor filled with a platinum-based catalyst as a combustion catalyst was used. As the flow pipe 14, a stainless steel pipe (inner diameter: 10 mm, total length: 20 m) having a spiral shape in part was used. As the heat storage material 15, about 25 liters (filling height: 900 mm) of ceramic balls (diameter: 6.35 mm) made of a mixture of aluminum oxide and silicon dioxide were filled in the main body container 11. The main body container 21 of the reforming reactor 2 was composed of a stainless steel tube (outer diameter: 165 mm, inner diameter: 158 mm, full length: 750 mm). A heat insulating material for heat insulation was attached around the main body container 21. The reforming reaction unit 22 was filled with about 10 liters (filling height: 500 mm) of a pellet-shaped steam reforming catalyst having a particle size of 3.0 mm containing aluminum oxide, copper oxide, and zinc oxide. This catalyst also functions as a catalyst for the partial oxidation reforming reaction. As the heat exchanger 3, a plate heat exchanger (trade name: brazing plate heat exchanger, manufactured by Nisaka Seisakusho) was used. As the PSA separator 5, a three-column PSA hydrogen separator (trade name: PSA hydrogen gas generator, manufactured by Sumitomo Seika) was used. Each adsorption tower of this apparatus had a cylindrical shape with a diameter of 50 mm and a total length of 1000 mm, and each adsorption tower was filled with about 1.7 liters of zeolite adsorbent (packing height: 900 mm).

[Production of hydrogen]
In the hydrogen production of this example, methanol water (20 ° C.) having a methanol concentration of 58.7 wt% is supplied at a flow rate at which the supply amounts of methanol and water to the system are 0.42 kmol / h and 0.525 kmol / h. And introduced into the heat exchanger 3. In the heat exchanger 3, the methanol water was heated to 137 ° C. by heat exchange with the reformed gas from the reforming reactor 2. Oxygen was added to the methanol water after passing through the heat exchanger 3 at a flow rate of 0.20 kmol / h. This mixed raw material was introduced into the vaporizer 1 and heated to 250 ° C. in the vaporizer 1 to be in a vaporized state. The vaporized mixed raw material is introduced into the reforming reactor 2, and a reformed gas (250 ° C.) containing hydrogen is generated by an autothermal reforming reaction (reaction pressure: 0.9 MPa) in the reforming reaction unit 22. Occurred. This reformed gas was introduced into the heat exchanger 3 and the temperature was lowered to 40 ° C. by heat exchange with methanol water. This reformed gas was introduced into the gas-liquid separator 4 and the liquid components contained in the reformed gas were separated and removed. Thereafter, the reformed gas was introduced into the PSA separator 5. In the PSA separator 5, the hydrogen-enriched gas was taken out from the reformed gas. Further, the hydrogen-containing desorption gas discharged from the PSA separator 5 was introduced into the catalytic combustion section 13 of the vaporizer 1 and used as a fuel for heating and vaporizing the mixed raw material. In such hydrogen production of the present embodiment, the methanol reaction rate in the reforming reactor 2 is 97.6%, the hydrogen recovery rate in the PSA separator 5 is 80%, and the hydrogen purity in the hydrogen-enriched gas is 99%. It was .999%. The acquisition amount of the hydrogen-enriched gas having a purity of 99.999% was 20.24 Nm ³ / h.

In this example, the proportion of the partial oxidation reforming reaction in the autothermal reforming reaction was about 20% by setting the oxygen supply rate to 0.20 kmol / h with respect to the methanol supply rate of 0.42 kmol / h. . In addition, by attaching a heat insulating material around the main body container 21 of the reforming reactor 2, heat dissipation from the main body container 21 was suppressed. Therefore, the heat balance between the endothermic amount (Q ₁ ) due to the steam reforming reaction in the reforming reactor 2 and the exothermic amount (Q ₂ ) due to the partial oxidation reforming reaction becomes almost zero, and a reformer is provided with a separate heating device or the like. There was no need to heat reactor 2.

  Further, in this example, the total amount of heat (48000 kJ / h) required to heat the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rate to be in a vaporized state is obtained in the heat exchanger 3. Approximately 50% of the amount of heat (15800 kJ / h) obtained from the reformed gas and the amount of heat (64500 kJ / h) generated by burning the hydrogen-containing desorption gas discharged from the PSA separator 5 in the catalytic combustion unit 13 ( 32200 kJ / h). Therefore, by supplying methanol and water as raw materials from 20 ° C. to 250 ° C. at the above flow rates, fuel is supplied from outside the system in order to obtain the total amount of heat (48000 kJ / h) required for vaporization. There was no need to keep burning.

Using the same hydrogen production system X1 as in Example 1, hydrogen (hydrogen-enriched gas) was produced from a mixed raw material (including methanol, water, and oxygen) in a raw material supply mode different from that in Example 1. Specifically, in the hydrogen production of this example, methanol water (20 ° C.) with a methanol concentration of 58.7 wt% was used, and the supply amounts of methanol and water to the system were 0.45 kmol / h and 0.5625 kmol. It was introduced into the heat exchanger 3 at a flow rate of / h. Air was added to the methanol water after passing through the heat exchanger 3 at a flow rate of 1.02 kmol / h. Other operations are the same as those in the first embodiment. In such hydrogen production in this example, the methanol reaction rate in the reforming reactor 2 is 97.6%, the hydrogen recovery rate in the PSA separator 5 is 75%, and the hydrogen purity in the hydrogen-enriched gas is 99. 0.9%. The acquisition amount of hydrogen-enriched gas having a hydrogen purity of 99.9% was 20.33 Nm ³ / h.

In this example, the ratio of the partial oxidation reforming reaction in the autothermal reforming reaction was about 20% by setting the air supply rate to 1.02 kmol / h with respect to the methanol supply rate of 0.45 kmol / h. . In addition, by attaching a heat insulating material around the main body container 21 of the reforming reactor 2, heat dissipation from the main body container 21 was suppressed. Therefore, the heat balance between the endothermic amount (Q ₁ ) due to the steam reforming reaction in the reforming reactor 2 and the exothermic amount (Q ₂ ) due to the partial oxidation reforming reaction becomes almost zero, and a reformer is provided with a separate heating device or the like. There was no need to heat reactor 2.

  Further, in this embodiment, the total amount of heat (51300 kJ / h) necessary for heating the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rate to be in a vaporized state is obtained in the heat exchanger 3. About 41% of the amount of heat (16000 kJ / h) obtained from the reformed gas and the amount of heat (86000 kJ / h) generated by burning the hydrogen-containing desorption gas discharged from the PSA separator 5 in the catalytic combustion unit 13 ( 35300 kJ / h). Therefore, in order to obtain the total amount of heat (51300 kJ / h) necessary for heating the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rates to make them vaporized, fuel from the outside of the hydrogen production system X1 There was no need to supply.

  Hydrogen (hydrogen-enriched gas) was produced from a mixed raw material (including methanol, water, and oxygen) in a raw material supply mode different from Examples 1 and 2, using a hydrogen production system X2A different from Examples 1 and 2. .

  In the hydrogen production system X2A of the present embodiment, by providing the tube body 23 inside the main body container 21 of the reforming reactor 2, the reforming reaction unit 22A is replaced with the reforming reaction unit 22 of the hydrogen production system X1. It was set as the structure to comprise. The tube body 23 was composed of a stainless steel tube (outer diameter: 114 mm, inner diameter: 110 mm, full length: 600 mm). Accordingly, the location where the reformed gas outlet 212 is disposed and the piping 68 connected to the reformed gas outlet 212 are changed as appropriate. In the first region 221 and the second region 222 as the reforming reaction section 22A, about 10 liters (filling height: 500 mm) of the same reforming catalyst as used in the above example was filled. The other configuration is the same as the hydrogen production system X1 of the first and second embodiments.

In the hydrogen production of this example, methanol water (20 ° C.) having a methanol concentration of 58.7 wt% is supplied at a flow rate at which the supply amounts of methanol and water to the system are 0.45 kmol / h and 0.5625 kmol / h. And introduced into the heat exchanger 3. Air was added to the methanol water after passing through the heat exchanger 3 at a flow rate of 1.02 kmol / h. Other operations are the same as those in the first embodiment. In such hydrogen production of the present embodiment, the methanol reaction rate in the reforming reactor 2A is 97.6%, the hydrogen recovery rate in the PSA separator 5 is 75%, and the hydrogen purity in the hydrogen-enriched gas is 99. 9%. The acquisition amount of hydrogen-enriched gas having a purity of 99.9% was 20.33 Nm ³ / h.

In this example, the ratio of the partial oxidation reforming reaction in the autothermal reforming reaction was about 20% by setting the air supply rate to 1.02 kmol / h with respect to the methanol supply rate of 0.45 kmol / h. . Moreover, the heat radiation from the main body container 21 was suppressed by attaching a heat insulating material around the main body container 21 of the reforming reactor 2A. Accordingly, the heat balance between the endothermic amount (Q ₁ ) due to the steam reforming reaction in the reforming reactor 2A and the exothermic amount (Q ₂ ) due to the partial oxidation reforming reaction becomes almost zero, and a reformer is provided with a separate heating device or the like. There was no need to heat reactor 2A.

  Further, in this embodiment, the total amount of heat (51300 kJ / h) necessary for heating the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rate to be in a vaporized state is obtained in the heat exchanger 3. About 41% of the amount of heat (16000 kJ / h) obtained from the reformed gas and the amount of heat (86000 kJ / h) generated by burning the hydrogen-containing desorption gas discharged from the PSA separator 5 in the catalytic combustion unit 13 ( 35300 kJ / h). Therefore, in order to obtain the total amount of heat (51300 kJ / h) required for heating the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rates to make them vaporized, fuel from the outside of the hydrogen production system X2A There was no need to supply and continue burning.

  Hydrogen (hydrogen-enriched gas) is obtained from a mixed raw material (including methanol, water, and oxygen) in a raw material supply mode different from that in Example 3, using a hydrogen production system X2C having a reformer different from that in Example 3. Manufactured.

  In the hydrogen production system X2C of this example, the tube body 23 provided inside the main body container 21 of the reforming reactor 2 is composed of seven stainless tubes (outer diameter: 50 mm, inner diameter: 48 mm, total length: 600 mm). In this configuration, a reforming reaction unit 22C is provided instead of the reforming reaction unit 22A of the hydrogen production system X2A. Other configurations are the same as the hydrogen production system X2A of the third embodiment.

In the hydrogen production of this example, methanol water (20 ° C.) having a methanol concentration of 58.7 wt% is supplied at a flow rate at which the supply amounts of methanol and water to the system are 0.42 kmol / h and 0.525 kmol / h. And introduced into the heat exchanger 3. Oxygen was added to the methanol water after passing through the heat exchanger 3 at a flow rate of 0.2 kmol / h. Other operations are the same as those in the first embodiment. In such hydrogen production of the present embodiment, the methanol reaction rate in the reforming reactor 2C is 97.6%, the hydrogen recovery rate in the PSA separator 5 is 80%, and the hydrogen purity in the hydrogen-enriched gas is 99. 999%. The acquisition amount of hydrogen-enriched gas having a hydrogen purity of 99.999% was 20.24 Nm ³ / h.

In this example, the oxygen supply rate was 0.2 kmol / h with respect to the methanol supply rate of 0.42 kmol / h, so that the proportion of the partial oxidation reforming reaction in the autothermal reforming reaction was about 20%. . Moreover, the heat dissipation from the main body container 21 was suppressed by attaching a heat insulating material around the main body container 21 of the reforming reactor 2C. Accordingly, the heat balance between the endothermic amount (Q ₁ ) due to the steam reforming reaction in the reforming reactor 2C and the exothermic amount (Q ₂ ) due to the partial oxidation reforming reaction becomes almost zero, and a reformer is provided with a separate heating device or the like. There was no need to heat reactor 2C.

  Further, in this example, the total amount of heat (48000 kJ / h) required to heat the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rate to be in a vaporized state is obtained in the heat exchanger 3. Approximately 50% of the amount of heat (15800 kJ / h) obtained from the reformed gas and the amount of heat (64500 kJ / h) generated by burning the hydrogen-containing desorption gas discharged from the PSA separator 5 in the catalytic combustion unit 13 ( 32200 kJ / h). Therefore, in order to obtain the total amount of heat (48000 kJ / h) necessary for heating the raw materials methanol and water from 20 ° C. to 250 ° C. at the above flow rates to bring them into a vaporized state, fuel is supplied from the outside of the hydrogen production system X2C. There was no need to supply.

[Temperature distribution in the reforming reaction section]
In Examples 3 and 4, the temperature distributions of the reforming reaction units 22A and 22C at the time of steady operation after one hour or more from the start of operation of the hydrogen production systems X2A and X2C were investigated. The investigation of the temperature distribution of the reforming reaction units 22A and 22C was performed by measuring the temperature at a plurality of measurement points set in the reforming reaction units 22A and 22C. In Example 3, the measurement point was set by being displaced on predetermined axes S1 and S2 along the gas flow direction in the first region 221 and the second region 222 (see FIGS. 4A and 4B). . In the reforming reaction part 22A, a thermometer was arranged so as to be movable along the axes S1 and S2. And the position of the measurement part of the said thermometer was sequentially shifted to the measurement point displaced on the axis | shaft S1 thru | or the axis | shaft S2, and the temperature for every said measurement point was measured. In Example 4, the measurement point was set to be displaced on predetermined axes S3 and S4 (see FIGS. 6A and 6B) along the gas flow direction in the first region 221 and the second region 222. In the reforming reaction part 22C, a thermometer was arranged so as to be movable along the axes S3 to S4. And the position of the measurement part of the said thermometer was sequentially shifted to the measurement point displaced on the axis | shaft S3 thru | or the axis | shaft S4, and the temperature for every said measurement point was measured.

  FIG. 10 is a graph showing the temperature distribution in the reforming reaction section. The horizontal axis in the figure represents the path length of 1000 mm in the gas flow direction of the reforming reaction sections 22A and 22C (500 mm which is the charging height of the reforming catalyst in the first region 221 and the reforming catalyst in the second region 222). (Total of 500 mm which is the filling height) represents the amount of displacement from the upstream end of the first region 221 to the measurement point in the gas flow direction as a base point. The vertical axis in the figure represents the measurement temperature at the measurement point. As clearly shown in FIG. 10, the temperature of the measurement point is within a relatively small range of 240 ° C. to 270 ° C. in Example 3 and 240 ° C. to 265 ° C. in Example 4, and the reforming reaction section 22A. , 22C, it was confirmed that the temperature of each part was leveled. This is considered to be because heat energy generated by the partial oxidation reforming reaction mainly proceeding in the first region 221 is transmitted to the second region 222 via the tube body 23. In Example 4, since a plurality (seven) of tube bodies 23 are provided, a larger heat receiving area is secured than in the case of providing one tube body 23 as in Example 3, and reforming is performed. The temperature distribution range of the reaction part 22C became smaller.

Claims (16)

A vaporizer for heating a mixed raw material containing a hydrocarbon-based raw material, water and oxygen into a vaporized state;
For generating a reformed gas containing hydrogen from the vaporized mixed raw material by causing a partial oxidation reforming reaction of the hydrocarbon raw material together with a steam reforming reaction of the hydrocarbon raw material. A reforming reactor,
By the pressure fluctuation adsorption type gas separation method performed using an adsorption tower filled with an adsorbent, the reformed gas is introduced into the adsorber tower to adsorb unnecessary components in the reformed gas to the adsorbent, A hydrogen-enriched gas is led out from the adsorption tower, the unnecessary component is desorbed from the adsorbent, and a hydrogen-containing desorption gas containing hydrogen remaining in the adsorption tower and the unnecessary component is discharged from the adsorption tower. A pressure fluctuation adsorption gas separation device for
The said vaporizer burns the said hydrogen-containing desorption gas, The said mixed raw material is heated by using the combustion gas produced by the said combustion as a heat source, The hydrogen production system characterized by the above-mentioned.   The hydrogen production system according to claim 1, wherein the hydrocarbon-based raw material is methanol.   2. The heating apparatus according to claim 1, further comprising heating means for heating the hydrocarbon-based raw material and the water before being supplied to the vaporizer, using the reformed gas from the reforming reactor as a heat source. Hydrogen production system.   The hydrogen production system according to claim 1, wherein the vaporizer has a catalytic combustion unit for catalytic combustion of the hydrogen-containing desorption gas.   The hydrogen production system according to claim 1, wherein the vaporizer has a heat storage unit for storing thermal energy of the combustion gas.   The vaporizer feeds the combustion gas into the main body container by catalytically burning the main body container, a flow pipe for passing the mixed raw material through the main body container, and the hydrogen-containing desorption gas. The hydrogen production system according to claim 1, further comprising: a catalytic combustion unit.   The hydrogen production system according to claim 6, wherein the vaporizer further includes a heat storage material filled in the main body container for storing thermal energy of the combustion gas.   The hydrogen production system according to claim 7, wherein the heat storage material is a ceramic ball.   The hydrogen production system according to claim 6, wherein the flow pipe has a spiral shape.   The hydrogen production system according to claim 1, further comprising heating means for heating the reforming reactor using the combustion gas as a heat source. The reforming reactor has an upstream first region and a downstream second region,
2. The hydrogen production system according to claim 1, wherein the first region and the second region are disposed adjacent to each other with a thermally conductive partition interposed therebetween. A reformer for generating a reformed gas by reforming a hydrocarbon-based material,
A vaporizer for heating a mixed raw material containing a hydrocarbon-based raw material, water, and oxygen to a vaporized state using combustion gas generated by burning fuel as a heat source;
For generating a reformed gas containing hydrogen from the vaporized mixed raw material by causing a partial oxidation reforming reaction of the hydrocarbon raw material together with a steam reforming reaction of the hydrocarbon raw material. And a reforming reactor. The reforming reactor has an upstream first region and a downstream second region,
The reforming apparatus according to claim 12, wherein the first region and the second region are disposed adjacent to each other with a thermally conductive partition interposed therebetween.   The reformer according to claim 12, wherein the fuel includes a part of the hydrogen in the reformed gas. A reformer for generating a reformed gas by reforming a hydrocarbon-based material,
By mixing the mixed raw material containing the hydrocarbon raw material in vaporized state, water and oxygen with the same catalyst together with the steam reforming reaction of the hydrocarbon raw material and the partial oxidation reforming reaction of the hydrocarbon raw material, A reforming reactor for generating a reformed gas containing hydrogen from the mixed raw material in the vaporized state,
The reforming reactor has an upstream first region and a downstream second region,
The reforming apparatus, wherein the first region and the second region are disposed adjacent to each other with a thermally conductive partition interposed therebetween.   The reforming apparatus according to claim 15, wherein the partition wall is composed of at least one tubular body.

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